3-perfluoroalkyl-5-substituted-oxy-isoxazole derivatives, process for preparing the same, and herbicides containing the same

ABSTRACT

A novel herbicidal compound of the formula: ##STR1## in which R is OH, C 1  -C 3  alkoxy or R 3  -N-R 4  ; R f  is C 1  -C 3  perfluoroalkyl; R 1  is hydrogen, C 1  -C 6  alkyl or optionally substituted phenyl; R 2  is hydrogen or C 1  -C 3  alkyl; n is an integer of 0 to 2; R 3  is hydrogen or C 1  -C 3  alkyl; R 4  is C 1  -C 6  alkyl, optionally substituted phenylalkyl where alkyl contains 1 to 3 carbons or optionally substituted phenyl; or R 3  and R 4  together with the nitrogen atom to which they are attached form a cyclic amino group; or a salt thereof. A process for preparing the compound (I) and a herbicide containing the compound (I) are also disclosed.

FIELD OF THE INVENTION

This invention relates to novel 3-perfluoroalkyl-5-substituted-oxy-isoxazoles, a process for producing them, and their use as herbicides.

BACKGROUND OF THE INVENTION

Some azole derivatives have been provided as herbicides. For example, Japanese Patent Laid Open Publication No. 147267/1980 discloses azolyloxy-carboxylic acid amides of the formula: ##STR2## and their use as herbicides. EP-A-18497 discloses compounds having substituted acetic acid anilide structure of the formula: ##STR3## and their use as herbicides. EP-A-94541 discloses substituted 5-trifluoromethyl-1,3,4-thiadiazole-2-yl-oxy-acetic acid amides of the formula: ##STR4## and their use as herbicides. However, no literature has disclosed 3-perfluoroalkyl-5-substituted-oxy-isoxaozle derivatives.

It has been found that the 3-perfluoroalkyl-5-substituted-oxy-isoxaozle derivatives show a high selectivity, specifically on pre-emergence application, and herbicidal activity without producing any material phytotoxicity on various agricultural crops such as rice, wheat, soybean, cotton and the like.

SUMMARY OF THE INVENTION

The present invention provides compounds of the formula: ##STR5## in which R is OH, C₁ -C₃ alkoxy or R³ -N-R⁴ ; R_(f) is C₁ -C₃ perfluoroalkyl; R¹ is hydrogen, C₁ -C₆ alkyl or optionally substituted phenyl; R² is hydrogen or C₁ -C₃ alkyl; n is an integer of 0 to 2; R³ is hydrogen or C₁ -C₃ alkyl; R⁴ is C₁ -C₆ alkyl, optionally substituted phenylalkyl where alkyl contains 1 to 3 carbons or optionally substituted phenyl; or R³ and R⁴ together with the nitrogen atom to which they are attached from a cyclic amino group; or a salt thereof, a process for producing them and their use as herbicides.

DISCLOSURE OF THE INVENTION

In the above formula (I), example of C₁ -C₃ alkoxy for R includes methoxy, ethoxy, isopropoxy etc. Example of C₁ -C₃ perfluoroalkyl for R_(f) includes trifluoromethyl, pentafluoroethyl, heptafluoropropyl etc. Example of C₁ -C₆ alkyl for R¹ includes methyl, ethyl, propyl, cyclohexyl etc. Example of optionally substituted phenyl includes phenyl, 4-fluorophenyl, 4-chlorophenyl, 4-methylphenyl, 4-methoxyphenyl, 3,4-dimethoxyphenyl, 3,4methylenedioxyphenyl etc. Example of C₁ -C₃ alkyl for R² includes methyl, ethyl, isopropyl etc. Example of C₁ -C₆ alkyl for R³ or R⁴ includes methyl, ethyl, propyl, isopropyl, isobutyl, hexyl, cyclohexyl etc. Example of optionally substituted phenylalkyl, where alkyl contains includes C₁ -C₃ carbons, includes benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, phenylpropyl etc. Example of optionally substituted phenyl includes phenyl, 2-methylphenyl, 3-methylphenyl, 4-ethyl-ethylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 3-trifluoromethylphenyl, 3,5-dichlorophenyl, 3-methylthiophenyl, 3-nitrophenyl etc. Example of a cyclic amino group for R³ and R⁴, formed together with nitrogen atom to which they are attached, includes 2-methylpiperidino, 2-ethylpiperidino, morpholino, pyrrolidino etc.

3-Perfluoroalkyl-5-substituted-oxy-isoxazole derivatives of the present invention can be prepared by the following procedure.

(a) It can be prepared by the reaction of a compound of formula: ##STR6## in which R_(f) and R¹ are as defined above and M is hydrogen or alkali metal atom, with a compound of the formula: ##STR7## in which R, R², R³, R⁴ and n are as defined above and Hal is halogen, in the presence of a basic substance in an inert solvent as necessary, at 0°-150° C., preferably at 30°-100° C., for 2-200 hours, preferably for 8-100 hours and the treatment of the resulting product by conventional techniques.

Example of the inert solvent includes acetonitrile, toluene, dioxane, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, acetone, methyl ethyl ketone etc.

Example of alkali metal atom for M includes sodium, potassium, lithium etc.

Example of halogen for Hal includes chlorine, bromine etc.

(b) It can be prepared by the reaction of a compound of the formula: ##STR8## in which R_(f), R¹, R² and n are as defined above, with a compound of the formula: ##STR9## in which R³ and R⁴ are as defined above, in the presence of a condensing agent in an inert solvent as necessary, at 0°-100° C., preferably at 20°-70° C., for 0.1-50 hours, preferably for 0.5-20 hours and the treatment of the resulting product by conventional techniques.

Example of the inert solvent includes tetrahydrofuran, dioxane etc. Example of the condensing agent includes DCC, polyphosphoric acid etc.

(c) It can be prepared by the reaction of a compound of the formula: ##STR10## in which R_(f), R¹ and Hal are as defined above, with a compound of the formula: ##STR11## in which R, R², R³, R⁴ and n are as defined above, in the presence of a basic substance in an inert solvent as necessary, at 0°-100° C., preferably at 20°-80° C. for 2-50 hours, preferably for 8-24 hours and the treatment of the resulting product by conventional techniques.

Example of an inert solvent includes tetrahydrofuran, dioxane, toluene etc. Example of a basic substance includes potassium t-butoxide, sodium hydrate etc. Example of halogen for Hal includes chlorine, bromine etc.

The compounds of the formula (III) and (V)-(VII) used as the starting material is known or can be made by known method.

The compound of the formula (II) can be prepared by the method described in EP-A-220025. The preparation method of the compound of the formula (IV) has been described in Preparation 3.

When the compound (I) of the present invention is used as the active ingredient of a herbicide, the dosage rate may vary on the purpose of use, weed species, the dosage rate is from 0.1 to 50 g, preferably from 1 to 30 g, of the active ingredient per are and the formulation may be applied as such without dilution or with dilution.

On the practical usage of the presently invented compound (I) as a herbicide, it may be applied in any preparation form such as dust, granules, an emulsion, wettable powder, a suspension and the like in combination with, as necessary, a conventional solid or liquid carrier, a combination carrier of conventional solid and liquid carriers, a surface active agent and/or an auxiliary agents.

The content of the present compound (I) as the active ingredient in said preparation form may be usually within a range of 1 to 80% by weight, preferably of 1 to 50% by weight.

As the solid carrier or diluent, there may be used clay (e.g. kaolin clay, attapulgite clay) bentonite, terra alba, pyrophyllite, talc, diatomaceous earth, silica, calcite, wallnut-shell powder, urea, ammonium sulfate, synthetic hydrated silica, etc. Example of the liquid carrier or diluent are water, aromatic hydrocarbons (e.g. benzene, toluene, xylene, methylnaphthalene), alcohols (e.g. isopropanol, ethylene glycol, cellosolve), ketones (e.g. acetone, cyclohexanone, isophorone), vegetable oils (e.g. soybean oil, cotton-seed oil), dimethyl sulfoxide, acetonitrile, cyclohexane, etc.

Examples of the surface active agent are the anionic type such as alkylsulfates, alkylarylsulfonates, dialkylsulfosuccinates, phosphates of polyoxyethylenealkylaryl ethers, etc. and the non-ionic type such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene black copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. The surface active agents have the actions such as emulsification, dispersion and wetting.

According to the purpose of an application, there can be added suitable auxiliaries such as emulsifiers, stabilizers, dispersing agents, suspension, spreaders, penetrating agents, wetting agents and the like, for example, ligninsulfonates, alginates, polyvinylalcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate), polyoxyethylene resin acid esters, abietates, dinaphthylmethanedisulfonates etc.

In general, the presently invented compounds formulated in any suitable formulation form are used by soil or foliar treatment. When the formulation is used by soil treatment, it is spread over the soil surface (if necessary, incorporated it into the soil). Examples of the soil applied are sandy loam, usual soil such as loamy soil, clayey soil, sandy soil and the like. The present compounds may be used together with other herbicides to improve their activity as herbicides, and in some cases, a synergistic effect can be expected. Further, they may be applied in combination with insecticides, acaricides, nematocides, fungicides, plant growth regulators, fertilizers, soil improvers, etc.

The following examples, preparations and formulation examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof.

Example 1

N-Methyl-N-(3-methylphenyl)-2-(3-trifluoromethyl-5-isoxazolyloxy)acetamide

To 2.23 g (10 mmole) of 3-trifluoromethyl-5-hydroxy isoxazole sodium salt (purity 78.6%) were added dry acetonitrile (35 ml) and N-methyl-N-(3-methylphenyl)-2-bromoacetamide (3.15 g) and the resulting mixture was stirred at 60° C. for 24 hours. The reaction solution was evaporated under reduced pressure and the residue was mixed with water (35 ml), extracted with methylene chloride, treated with anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by chromatography on silica gel to give 2.09 g of crystals. After these were dissolved in benzene, n-hexane was added gradually and the precipitated crystals were filtered off to give 1.96 g of the tilted compound as colorless prisms, yield 62.4%, m.p. 54.0°-55.5° C.

Anal. Calcd. for C₁₄ H₁₃ N₂ 0₃ F₃ : C, 53.51; H, 4.17; N, 8.91. Found C, 53.52; H, 4.11; N, 8.82.

Example 2

N-Ethyl-N-phenyl-2-(3-trifluoromethyl-5-isoxazolyloxy)acetamide

(i) To 1.80 g (8.0 mmole) of methyl 2-(3-trifluoromethyl-5-isoxazolyloxy)acetate was added a 1% solution of NaOH (38.40 g, 9.6 mmole) and the resulting mixture was stirred at room temperature for one hour. After being adjusted to pH 1 with conc. HCl with ice cooling, the solution was extracted with diethyl ether. The ether layer was dried with anhydrous sodium sulfate and diethyl ether was evaporated under reduced pressure to give 1.68 g of colorless crystals. These were recrystallized from benzenecyclohexane to give 1.60 g of 2-(3-trifluoromethyl-5-ixoxazolyloxy)acetic acid as colorless plates, yield 94.7%, m.p. 99.0°-100° C.

Anal. Calcd. for C₆ H₄ NO₄ F₃ : C, 34.14; H, 1.19; N, 6.64. Found: C, 33.85; H, 2.13; N, 7.13.

(ii) 1.30 ml (2.37 mmole) of N-ethylaniline and 0.50 g (2.37 mmole) of 2-(3-trifluoromethyl-5-isoxazolyloxy)acetic acid were dissolved in 2.4 ml of dry THF and to the solution was added 0.60 g (2.61 mmole) of dicyclohexylcarbodiimide. After being stirred at room temperature for one hour, the reaction mixture was allowed to stand overnight at room temperature. After the addition of glacial acetic acid (0.2 ml), the mixture was stirred at room temperature for 30 minutes and the precipitated crystals were filtered off. The filtrate was evaporated under reduced pressure and the residue was purified by chromatography on silica gel to give 638 mg of the titled compound as a pale red viscous liquid, yield 85.7%.

IR(CHCl₃ ; cm⁻¹): 1680, 1610, 1494.

Anal. Calcd. for C₁₄ H₁₃ N₂ O₃ F₃ : C, 53.51; H, 4.17; N, 8.91. Found: C, 54.06; H, 4.32; N, 9.15

Example 3

N-Methyl-N-phenyl-2-(3-trifluoromethyl-4-phenyl-5-isoxazolyloxy)acetamide

0.99 g (6.0 mmole) of N-methyl-N-phenyl-2-hydroxyacetamide was dissolved in THF (6 ml) and the solution was mixed with 0.75 g (6.0 mmole) of 90% potassium t-butoxide with ice cooling. The mixture was stirred for 30 minutes and then 1.24 g (5.0 mmole) of 3-trifluoromethyl-4-phenyl-5-chloroisoxazole was added dropwise to the mixture. After being stirred for 30 minutes, the mixture was refluxed for 24 hours. After cooling the reaction mixture, 60 ml of methylene chloride was added and the mixture was washed with a 5% solution of HCl and water. The methylene chloride phase was evaporated under reduced pressure and the residue was purified by chromatography on silica gel to give 1.15 g of colorless crystals. These were recrystallized from n-hexane to give 950 mg of the titled compound, yield 50.5%, m.p. 93.0°-94.0° C.

Anal. Calcd. for C₉ H₁₅ N₂ O₃ F₃ : C, 60.63; H, 4.03; N, 7.44; F, 15.15. Found: C, 61.01; H, 4.35; N, 7.39; F, 15.22.

Example 4

Methyl 2-(3-trifluoromethyl-4-methyl-5-isoxazolyloxy)acetate

To 1.00 g (6 mmole) of 3-trifluoromethyl-4-methyl-5-hydroxyisoxazole were added 10 ml of dry acetone and 1.00 g (7.2 mmole) of anhydrous potassium carbonate and the resulting mixture was stirred at room temperature for one hour. After addition of methyl bromoacetate (1.10 g, 7.2 mmole), the mixture was refluxed for 30 hours. The reaction mixture was mixed with water (100 ml) and, extracted with diethyl ether. The diethyl ether phase was dried with anhydrous magnesium sulfate, evaporated under reduced pressure, and the residue was purified by chromatography on silica gel to give 0.73 g of the title compound as colorless viscous liquid, yield 53.6%.

Example 5 N-Methyl-N-phenyl-2-(3-pentafluoroethyl-5-isoxazolyloxy)acetamide

To 0.50 g (2.2 mmole) of 3-pentafluoroethyl-5-hydroxyisoxazole sodium salt were added dry acetonitrile (7 ml) and N-methyl-N-phenyl-2-bromoacetamide (0.55 g) and the resulting mixture was stirred at 60° C. for 24 hours. After completion of reaction, the reaction solution was evaporated under reduced pressure and to the residue was added water (80 ml), extracted with methylene chloride, treated with anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by chromatography on silica gel to give 0.52 g of crystals. These crystals were recrystallized from n-hexane to give 0.48 g of the titled compound as colorless plates, yield 62.3%, m.p. 88.0-89.0° C.

Anal. Calcd. for C₁₄ H₁₁ N₂ O₃ F₅ : C, 48.00; H, 3.17; N, 8.00. Found: C, 47.83; H, 3.32; N, 8.05.

Examples 6 to 128

The following compounds were prepared according to the same procedure as described in examples 1 to 5. The results are shown in Tables 1 and 2.

In the tables, boiling points (b.p.) were shown in °C./mmHg, melting points (m.p.) were shown in °C. and infrared spectra were measured in CHCl₃ and shown in cm⁻¹.

                                      TABLE 1                                      __________________________________________________________________________      ##STR12##                                                                     Ex.                           Yield                                                                              Physical                                     No.                                                                               R          n R.sup.2                                                                           R.sup.1    (%) property                                                                               Appearance                           __________________________________________________________________________     6  CH.sub.3 O 0 H  H          31.7                                                                               b.p:    colorless                                                              75-76/0.50                                                                             liquid                               7  HO         0 CH.sub.3                                                                          H          89.4                                                                               mp:     colorless                                                              56.0-58.0                                                                              needles                              8  CH.sub.3 O 0 CH.sub.3                                                                          H          79.4                                                                               IR:     colorless                                                              1756, 1160, 1100                                                                       liquid                               9  CH.sub.3 O 0 CH.sub.3                                                                          CH.sub.3   74.2                                                                               IR:     pale yellow                                                            1750, 1480, 1150                                                                       liquid                               10 CH.sub.3 O 0 CH.sub.3                                                                           ##STR13## 84.1                                                                               IR: 1756, 1480, 1150                                                                   colorless liquid                     11 CH.sub.3 O 0 CH.sub.3                                                                           ##STR14## 64.9                                                                               IR: 1750, 1485, 1150                                                                   pale yellow liquid                   12 CH.sub.3 O 0 CH.sub.3                                                                           ##STR15## 78.6                                                                               IR: 1755, 1485, 1180                                                                   colorless liquid                     13                                                                                 ##STR16## 0 H  H          46.2                                                                               IR: 1678, 1160, 1100                                                                   pale yellow liquid                   14                                                                                 ##STR17## 0 H  H          41.0                                                                               IR: 1665, 1160, 1100                                                                   pale yellow liquid                   15                                                                                 ##STR18## 0 H  H          54.7                                                                               IR: 1660, 1614, 1158                                                                   thin brown viscous liquid            16                                                                                 ##STR19## 0 H  H          39.6                                                                               IR: 1666, 1612, 1100                                                                   thin brown viscous liquid            17                                                                                 ##STR20## 0 H  H          17.5                                                                               IR: 1676, 1614, 1496                                                                   thin yellow green viscous                                                      liquid                               18                                                                                 ##STR21## 0 H  H          44.2                                                                               IR: 1663, 1612, 1096                                                                   thin yellow green viscous                                                      liquid                               19                                                                                 ##STR22## 0 H  H          61.6                                                                               IR: 1660, 1160, 1105                                                                   thin yellow green viscous                                                      liquid                               20                                                                                 ##STR23## 0 H  H          65.3                                                                               mp: 50.0-52.0                                                                          pale yellow prisms                   21                                                                                 ##STR24## 0 H                                                                                  ##STR25## 71.9                                                                               mp: 123.0-124.0                                                                        colorless prisms                     22                                                                                 ##STR26## 0 H                                                                                  ##STR27## 69.4                                                                               IR: 1660, 1490, 1152                                                                   colorless viscous liquid             23 HO         0 H  CH.sub.3   84.9                                                                               mp:     colorless plates                                                       77.0-78.0                                    24 HO         0 H                                                                                  ##STR28## 70.4                                                                               mp:  112.0-114.0                                                                       colorless prisms                     25                                                                                 ##STR29## 0 H                                                                                  ##STR30## 65.8                                                                               mp: 114.0-115.0                                                                        colorless prisms                     26                                                                                 ##STR31## 0 H  CH.sub.3   72.3                                                                               IR: 1680, 1490, 1150                                                                   pale yellow viscous liquid           27                                                                                 ##STR32## 0 H  CH.sub.3   98.4                                                                               IR: 1660, 1490, 1060                                                                   pale brown viscous                   __________________________________________________________________________                                               liquid                          

                                      TABLE 2                                      __________________________________________________________________________      ##STR33##                                                                     Ex.                                    Yield                                                                               Physical                           No.  R.sup.4   R.sup.3                                                                               n  R.sup.2                                                                           R.sup.1    (%)  property  Appearance               __________________________________________________________________________     28                                                                                   ##STR34##                                                                               CH.sub.3                                                                              0  H  H          39.1 mp: 67.0-68.0                                                                            colorless plates         29                                                                                   ##STR35##                                                                               CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           77.3 mp: 56.0-59.0                                                                            colorless crystals       30                                                                                   ##STR36##                                                                               CH.sub.3                                                                              0  H  H          60.8 mp: 52.5-53.5                                                                            colorless powder         31                                                                                   ##STR37##                                                                               CH.sub.3                                                                              0  CH.sub.3                                                                          H          56.5 IR: 1666, 1608,                                                                          colorless viscous                                                              liquid                   32                                                                                   ##STR38##                                                                               CH.sub.3                                                                              0  H  CH.sub.3   63.6 mp: 58.0-60.0                                                                            colorless crystals       33                                                                                   ##STR39##                                                                               CH.sub.3                                                                              0  CH.sub.3                                                                          CH.sub.3   80.4 IR: 1676, 1488,                                                                          colorless liquid         34                                                                                   ##STR40##                                                                               CH.sub.3                                                                              1  H                                                                                  ##STR41## 23.3 IR: 1640, 1494,                                                                          thin yellow viscous                                                            liquid                   35                                                                                   ##STR42##                                                                               CH.sub.3                                                                              0  CH.sub.3                                                                           ##STR43## 87.1 IR: 1674, 1490,                                                                          colorless viscous                                                              liquid                   36                                                                                   ##STR44##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR45## 65.7 mp: 90.0-91.0                                                                            colorless prisms         37                                                                                   ##STR46##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR47## 49.9 mp: 85.5-86.5                                                                            colorless prisms         38                                                                                   ##STR48##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR49## 69.0 mp: 84.0-84.5                                                                            colorless plates                                                               (efforescence)           39                                                                                   ##STR50##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR51## 50.5 mp: 92.5-93.0                                                                            colorless prisms         40                                                                                   ##STR52##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR53## 64.5 mp: 53.0-54.5                                                                            colorless solid          41                                                                                   ##STR54##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR55## 87.9 mp: 88.0-90.0                                                                            colorless crystals       42                                                                                   ##STR56##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR57## 75.1 mp: 79.0-79.5                                                                            colorless prisms         43                                                                                   ##STR58##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR59## 70.6 mp: 59.0-62.0                                                                            colorless solid          44                                                                                   ##STR60##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR61## 69.2 mp: 115.5-116.0                                                                          colorless needles        45                                                                                   ##STR62##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR63## 32.7 mp: 114.0-115.0                                                                          colorless needles        46                                                                                   ##STR64##                                                                                ##STR65##                                                                            0  H                                                                                  ##STR66## 66.7 mp: 155.0-156.0                                                                          colorless needles        47                                                                                   ##STR67##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR68## 56.7 mp: 100.0-101.5                                                                          colorless prisms         48                                                                                   ##STR69##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR70## 48.7 mp: 101.0-102.0                                                                          colorless needles        49                                                                                   ##STR71##                                                                               CH.sub.3                                                                              0  CH.sub.3                                                                           ##STR72## 45.5 mp: 90.5-92.0                                                                            colorless prisms         50                                                                                   ##STR73##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR74## 71.1 mp: 94.5-96.0                                                                            colorless  needles       51                                                                                   ##STR75##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR76## 62.8 mp: 97.0-98.0                                                                            colorless prisms         52                                                                                   ##STR77##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR78## 72.2 mp: 133.0-134.0                                                                          colorless prisms         53                                                                                   ##STR79##                                                                               CH.sub.3                                                                              0  CH.sub.3                                                                           ##STR80## 74.5 mp: 81.0-82.0                                                                            colorless prisms         54                                                                                   ##STR81##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR82## 27.5 mp: 104.0-105.0                                                                          colorless prisms         55                                                                                   ##STR83##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR84## 74.6 mp: 99.5-100.5                                                                           colorless prisms         56                                                                                   ##STR85##                                                                               CH.sub.3                                                                              0  H                                                                                  ##STR86## 67.8 mp:  128.0-130.0                                                                         pale yellow                                                                    crystals                 57                                                                                   ##STR87##                                                                               C.sub.2 H.sub.5                                                                       0  H  CH.sub.3   93.4 mp: 75.0-77.0                                                                            colorless prisms         58                                                                                   ##STR88##                                                                               n-C.sub.3 H.sub.7                                                                     0  H  CH.sub.3   97.8 mp: <30.0 IR: 1670, 1480,                                                      1140      pale yellow                                                                    crystals                 59                                                                                   ##STR89##                                                                               CH(CH.sub.3).sub.2                                                                    0  H  CH.sub.3   90.3 mp: 49.0-50.0                                                                            colorless crystals       60                                                                                   ##STR90##                                                                               n-C.sub.4 H.sub.9                                                                     0  H  CH.sub.3   93.5 IR: 1675, 1490,                                                                          colorless viscous                                                              liquid                   61                                                                                   ##STR91##                                                                               n-C.sub.5 H.sub.11                                                                    0  H  CH.sub.3   95.4 IR: 1670, 1480,                                                                          pale yellow viscous                                                            liquid                   62                                                                                   ##STR92##                                                                               CH.sub.3                                                                              0  H  CH.sub.3   86.4 mp: 81.0-82.0                                                                            colorless granular                                                             crystals                 63                                                                                   ##STR93##                                                                               CH.sub.3                                                                              0  H  CH.sub.3   77.9 mp: 86.0-88.0                                                                            colorless crystals       64                                                                                   ##STR94##                                                                               CH.sub.3                                                                              0  H  CH.sub.3   79.9 mp: 74.0-76.0                                                                            colorless crystals       65                                                                                   ##STR95##                                                                               CH.sub.3                                                                              0  H  CH.sub.3   90.6 mp: 82.0-84.0                                                                            colorless crystals       66                                                                                   ##STR96##                                                                               CH.sub.3                                                                              0  H  CH.sub.3   87.1 IR: 1675, 1488,                                                                          colorless viscous                                                              liquid                   67                                                                                   ##STR97##                                                                               CH.sub.3                                                                              0  H  CH.sub.3   96.3 IR: 1680, 1145,                                                                          colorless viscous                                                              liquid                   68                                                                                   ##STR98##                                                                               CH.sub.3                                                                              0  H  CH.sub.3   53.2 mp: 73.0-75.0                                                                            colorless crystals       69                                                                                   ##STR99##                                                                               CH.sub.3                                                                              0  H  CH.sub.3   75.1 mp: 92.0-94.0                                                                            colorless crystals       70                                                                                   ##STR100##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   89.9 mp: 36.0-39.0                                                                            colorless crystals       71                                                                                   ##STR101##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   77.9 IR: 1670, 1485,                                                                          colorless viscous                                                              liquid                   72                                                                                   ##STR102##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   96.8 IR: 1675, 1483,                                                                          colorless viscous                                                              liquid                   73                                                                                   ##STR103##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   83.2 mp: 66.0-67.0                                                                            colorless crystals       74                                                                                   ##STR104##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   95.4 mp: 44.0-46.0                                                                            pale yellow                                                                    crystals                 75                                                                                   ##STR105##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   80.2 mp: 84.0-85.0                                                                            colorless crystals       76                                                                                   ##STR106##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   88.3 mp: 50.0-52.0                                                                            pale yellow                                                                    crystals                 77                                                                                   ##STR107##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   95.6 mp:  65.0-67.0                                                                           colorless crystals       78                                                                                   ##STR108##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   66.4 mp: 94.0-95.0                                                                            colorless needles        79                                                                                   ##STR109##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   89.3 IR: 1675, 1490,                                                                          pale yellow viscous                                                            liquid                   80                                                                                   ##STR110##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   91.5 mp: 74.0-76.0                                                                            pale yellow                                                                    crystals                 81                                                                                   ##STR111##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   82.8 IR: 1670, 1495,                                                                          colorless  viscous                                                             liquid                   82                                                                                   ##STR112##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   86.2 mp: 50.0-52.0                                                                            colorless crystals       83                                                                                   ##STR113##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   89.8 mp: 99.0-101.0                                                                           colorless crystals       84                                                                                   ##STR114##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   83.5  mp: 93.0-95.0                                                                           colorless crystals       85                                                                                   ##STR115##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   77.9 mp: 66.0-68.0                                                                            colorless crystals       86                                                                                   ##STR116##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   94.0 mp: 113.0-114.5                                                                          colorless crystals       87                                                                                   ##STR117##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   83.1 mp: 74.0-76.0                                                                            colorless crystals       88                                                                                   ##STR118##                                                                              CH.sub.3                                                                              0  H  CH.sub.3   79.9 mp: 60.0-63.0                                                                            colorless crystals       89                                                                                   ##STR119##                                                                              CH.sub.3                                                                              0  H  n-C.sub.4 H.sub.9                                                                         45.6 IR; 1675, 1480,                                                                          colorless viscous                                                              liquid                   90                                                                                   ##STR120##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR121##                                                                               63.7 mp:  77.0-79.0                                                                           colorless crystals       91                                                                                   ##STR122##                                                                              C.sub.2 H.sub.5                                                                       0  H  H          85.7 IR: 1680, 1610,                                                                          red viscous liquid       92                                                                                   ##STR123##                                                                              CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           64.4 mp: 59.0-61.0                                                                            colorless crystals       93                                                                                   ##STR124##                                                                              CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           92.6 mp: 51.0-54.0                                                                            pale yellow                                                                    crystals                 94                                                                                   ##STR125##                                                                              CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           91.0 mp: 40.0-46.0                                                                            reddish brown                                                                  crystals                 95                                                                                   ##STR126##                                                                              C.sub.2 H.sub.5                                                                       0  H                                                                                  ##STR127##                                                                               95.1 mp: 97.0-99.0                                                                            colorless crystals       96                                                                                   ##STR128##                                                                              n-C.sub.3 H.sub.7                                                                     0  H                                                                                  ##STR129##                                                                               95.4 mp: 75.0-77.0                                                                            colorless crystals       97                                                                                   ##STR130##                                                                              CH(CH.sub.3).sub.2                                                                    0  H                                                                                  ##STR131##                                                                               81.2 mp: 85.0-87.0                                                                            colorless crystals       98                                                                                   ##STR132##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR133##                                                                               91.5 mp: 88.0-90.0                                                                            colorless crystals       99                                                                                   ##STR134##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR135##                                                                               91.4 mp: 82.9-84.0                                                                            pale yellow                                                                    crystals                 100                                                                                  ##STR136##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR137##                                                                               91.9 mp: 95.0-98.0                                                                            colorless crystals       101                                                                                  ##STR138##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR139##                                                                               91.8 mp: 114.0-115.0                                                                          colorless crystals       102                                                                                  ##STR140##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR141##                                                                               70.1 mp: 69.0-70.0                                                                            colorless crystals       103                                                                                  ##STR142##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR143##                                                                               71.7 mp: 101.0-103.0                                                                          colorless crystals       104                                                                                  ##STR144##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR145##                                                                               75.5 mp: 121.0-123.0                                                                          colorless crystals       105                                                                                  ##STR146##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR147##                                                                               76.1 mp: 68.0-72.0                                                                            colorless crystals       106                                                                                  ##STR148##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR149##                                                                               63.0 mp: 85.0-86.0                                                                            colorless crystals       107                                                                                  ##STR150##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR151##                                                                               79.0 mp: 41.0-43.0                                                                            pale yellow                                                                    crystals                 108                                                                                  ##STR152##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR153##                                                                               80.9 IR: 1675, 1485,                                                                          pale yellow viscous                                                            liquid                   109                                                                                  ##STR154##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR155##                                                                               77.7 mp: 76.5-79                                                                              colorless crystals       110                                                                                  ##STR156##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR157##                                                                               90.7 mp: 76.0-78.0                                                                            pale                                                                           brown crystals           111                                                                                  ##STR158##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR159##                                                                               84.8 mp: 53.0-55.0                                                                            pale yellow                                                                    crystals                 112                                                                                  ##STR160##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR161##                                                                               82.4 mp: 75.0-77.0                                                                            pale yellow                                                                    crystals                 113                                                                                  ##STR162##                                                                              H      0  CH.sub.3                                                                          CH.sub.3   47.7 mp: 82.0-84.0                                                                            colorless plates         114                                                                                  ##STR163##                                                                              H      0  H  CH.sub.3   71.0 mp: 88.0-89.0                                                                            colorless needles        115                                                                                  ##STR164##                                                                              H      0  H  CH.sub.3   78.9 mp:  84.0-85.0                                                                           colorless plates         116                                                                                  ##STR165##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR166##                                                                               95.1 mp: 71.0-73.0                                                                            colorless prisms         117                                                                                  ##STR167##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR168##                                                                               93.0 mp: 68.0-70.0                                                                            colorless crystals       118                                                                                  ##STR169##                                                                              CH.sub.3                                                                              0  H                                                                                  ##STR170##                                                                               84.5 IR: 1680, 1490,                                                                          colorless viscous                                                              liquid                   119                                                                                  ##STR171##                                                                              CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           98.2 IR: 1685, 1485,                                                                          pale brown viscous                                                             liquid                   120                                                                                  ##STR172##                                                                              CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           96.7 mp: 55.0-57.0                                                                            colorless crystals       121                                                                                  ##STR173##                                                                              CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           89.3 mp: 46.0-48.0                                                                            pale                                                                           brown crystals           122                                                                                  ##STR174##                                                                              CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           75.9 mp: 53.0-57.0                                                                            colorless needles        123                                                                                  ##STR175##                                                                              CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           91.7 mp: 75.0-77.0                                                                            colorless brown                                                                crystals                 124                                                                                  ##STR176##                                                                              CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           90.5 mp: 39.0-42.0                                                                            pale yellow                                                                    crystals                 125                                                                                  ##STR177##                                                                              CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           84.2 mp: 61.0-63.0                                                                            colorless crystals       126                                                                                  ##STR178##                                                                              CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           73.5 mp: 89.0-90.0                                                                            colorless plates         127                                                                                  ##STR179##                                                                              CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           89.6 IR: 1675, 1482,                                                                          pale yellow viscous                                                            liquid                   128                                                                                  ##STR180##                                                                              CH.sub.3                                                                              0  H  C.sub.2 H.sub.5                                                                           74.3 IR: 1680, 1485, 1150 mp:                                                       66.0-68.0 pale yellow              __________________________________________________________________________                                                           crystals            

Preparation 1 3-Trifluoromethyl-4-phenyl-5-chloroisoxazole

To 2.28 g (10.0 mmole) of 3-trifluoromethyl-4-phenyl-5-aminoisoxazole were added 20 ml of conc. HCl and 1.09 g (11. 0 mmole) of cuprous chloride and 4.2 ml of aqueous sodium nitrate (2.76 g, 40 mmole) was added dropwise to the reaction mixture, keeping the temperature at 20°-25° C. After addition, the temperature was raised to 40°-45° C. and the mixture was stirred for 1 hour. To the mixture was added 16 ml of water, extracted with methylene chloride, dried with anhydrous sodium sulfate, evaporated under reduced pressure. The residue was purified by chromatography on silica gel to give 0.5651 g of colorless liquid. This was distilled under reduced pressure to give 0.4193 g of the titled compound as colorless liquid, yield 16.9%, b.p. 80.0°-83.0° C./0.50 mmHg.

Anal. Calcd. for C₁₀ H₅ NOClF₃ : C, 48.51; H, 2.04; N, 5.66; Cl, 14.32. Found C, 48.29; H, 2.23; N, 5.75; Cl, 14.90.

Preparation 2 3-Trifluoromethyl-5-chloroisoxazole

The titled compound as tan liquid was prepared according to the same procedure as described in preparation 1, b.p. 70.0° C./5.0 mmHg.

Preparation 3 2-(3-Trifluoromethyl-4-methyl-5-isoxazolyloxy)acetic acid

To 4 ml of methanol were 0.73 g (3.2 mmole) of methyl 2-(3-trifluoromethyl-4-methyl-5-isoxazolyloxy) acetate and 6 ml of 2.5% aqueous NaOH (3.6 mmole) and the resulting mixture was stirred for 3 hours. To the reaction mixture was added 100 ml of 1% aqueous HCl, extracted with diethyl ether. The diethyl ether phase was dried with anhydrous sodium sulfate and evaporated under reduced pressure to give 0.65 g of the titled compound as pale yellow crystals, yield 90.2%, m.p. 73.5°-76.0° C.

IR(CHCl₃, cm⁻¹): 1750, 1660, 1490, 1300.

In the following examples wherein parts are by weight.

Formulation Example 1

Fifty parts of the compound (I) of the present invention, 3 parts of calcium ligninsulfonate, 5 parts of sodium laurylsulfate, 2 parts of white carbon and 40 parts of clay are well mixed while being powdered to obtain a wettable powder.

Formulation Example 2

Forty parts of the compound (I) of the present invention, 5 parts of polyoxyethylenestyrylphenyl ether, 3 parts of calcium dodecylbenzenesulfonate, 30 parts of xylene and 22 parts of cyclohexanone are well mixed to obtain an emulsifiable concentrate.

Formulation Example 3

Three parts of the compound (I) of the present invention, 3 parts of polyoxyethylenealkylsulfate, 2 parts of calcium ligninsulfonate, 20 parts of bentonite and 72 parts of kaolin clay are well mixed while being powdered. The mixture is then kneaded, granulated and dried to obtain granules.

Formulation Example 4

Thirty parts of the compound (I) of the present invention is mixed with 5 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 60 parts of water and pulverized until the particle size of the mixture becomes less than 2 microns to obtain a suspension.

It has now been found that the present compounds (I) showed a strong herbicidal activity against monocotyledonous and dicotyledonous weeds, of which typical examples in paddy fields are Gramineous weeds such as common barnyardgrass (Echinochloa oryzicola) broadleaf weeds such as pickerelweed (Monochoria vaginalis), Vandellia anagustifolia, toothcup (Rotala indica) and arrowhead (Sagittaria pygmaea); Cyperaceous weeds such as umbrella plant (Cyperus difformis), bulrush (Scirpus juncoides SUBSP.), slender spikerush (Eleocharis acicularis), waterchestnut (Eleocharis Kuroguwai) and perennial sedge (Cyperus serotinus); in upland fields are such as large crabgrass (Digitaria adscendens) and barnyardgrass (Echinochloa crus-galli). The herbicidal doses of the compounds (I) exert no or little phytotoxicity to useful plants such as rice plant, wheat, soybean and cotton, and the phytotoxicity is recoverable even if the compounds produce it. Accordingly, the present compounds (I) can be used as pre-emergence application herbicides and post-emergence application herbicides applicable to agricultural fields such as upland field, paddy field, pasture land, orchards, tea plantations, mulberry field and non-crop land as well as non-agricultural fields such as lawn, park green, woodland, man-made land, vacant land, hausing land, factory site, riverbed, railway and roadway.

Further, the present compounds (I), too, show a stable activity by soil incorporation, which the herbicidal effects of conventional herbicides are lowered in general. Particularly, in paddy field condition, the compounds (I) produces an enhanced residual effect and herbicidal activity, and the herbicidal spectrum of the compounds (I) can be enlarged, while the phytotoxicity to rice plants is much more reduced.

In addition, as the compounds (I) are non-toxic to human, domestic animals, fowls etc. and low fish toxicity, they are safety and do not cause any residual toxicity.

The biological effect of the present compounds (I) as herbicides will be illustratively shown in the following. Examples wherein the phytotoxicity to crop plants and the herbicidal activity on weeds were evaluated visually according to a score from 0 (no damage)-5 (complete kill).

Test Example 1

The test of herbicidal activity in paddy field

(1) Pre-emergence application

Paddy field soil were fed in Wagner's pots of 1/10000 are and the pots were saturated with water. Thereafter, rice seedlings (Nihonbare) in 2.5-leaf stage were transplanted. In addition, seeds of barnyardgrass, umbrella plant, pickerelweed, Vandellia and toothcup were planted therein.

On 7th day of the transplanting (two days after the sowing: pre-emergence), a designed amount of the test compound was diluted with 5 ml per pot of water and the dilution was added dropwise with pipet to the water of the pot. After the treatment, the test plants were grown for three weeks in a greenhouse, and the herbicidal activity and the phytotoxicity were examined. The results are shown in Table 3 and 4.

(2) Pre-emergence application

Paddy field soil were fed in Wagner's pots of 1/10000 are and the pots were saturated with water. Thereafter, rice seedlings (Nihonnbare) in 2.5-leaf stage were transplanted. In addition, seeds of slender spikerush, water chestnut, nutsedge, arrowhead, bog pondweed and bulrush were planted therein.

On 7th day of the transplanting (two days after the sowing: pre-emergence), a designed amount of the test compound was diluted with 5 ml per pot of water and the dilution was added dropwise with pipet to the water of the pot. After the treatment, the test plants were grown for four weeks in a greenhouse, and the herbicidal activity and the phytotoxicity were evaluated. The results are shown in Table 5.

(3) Post-emergence application

Paddy field soil were fed in Wagner's pots of 1/10000 are and the pots were saturated with water. Thereafter, rice seedlings (Nihonbare) in 2.5-leaf stage were transplanted. In addition, seeds of common barnyardgrass, umbrella plant, pickerelweed, Vandellia and toothcup were sown therein.

On 14th day of the transplantation (eight days after the sowing: post-emergence), a designed amount of the test compound was diluted with 5 ml per pot of water and the dilution was added dropwise with pipet to the surface of the pot. After the treatment, the test plants were grown for three weeks in a greenhouse, and the herbicidal activity and the phytotoxicity were evaluated. The results are shown in Tables 6 and 7.

Test example 2

The test of herbicidal activity in upland field

(1) Pre-emergence application

Upland field soil were fed in square-shaped polyvinyl pots (10×10 cm² (area)). 20 seeds of large crabgrass, barnyardgrass, pale smartweed and green amaranth, respectively, were planted in 0.5 cm soil depth in a pot and 5-10 seeds of corn, wheat, soybean, cotton, beat, rape and tomato in 1 cm depth.

Immediately thereafter, a designed amount of the test compound was diluted with 10 1 per are of water and then Tween-20 (available from Nakarai Chemical Co.) corresponding to the amount of 100 ppm was added therein, and the dilution was sprayed uniformly onto the soil by means of an automatic pressure sprayer. After the treatment, the test plants were grown for four weeks in a greenhouse at 25° C., and the herbicidal activity on various weed plants and the phytotoxicity to crop plants were evaluated. The results are shown in Tables 8 and 9.

(2) Post-emergence application

Upland field soil were fed in polyvinyl pots (10×10 cm² (area)). 20 seeds of large crabgrass, barnyardgrass, pale smartweed and green amaranth, respectively, were planted in a pot and 5-10 seeds of corn, wheat, soybean, cotton, beat, rape and tomato, respectively, and they were grown in a green-house. Seven days after the planting at 2 leaf stage of large crabgrass (barnyardgrass, 2 leaf stage; pale smartweed and green amaranth, 1 leaf stage; beat, rape and tomato, cotyledon stage), a designed amount of the test compound was diluted with 10 1/are of water containing Tween -20 corresponding to the amount of 100 ppm as a spreading agent and sprayed to the foliage of the test plants. After the treatment, the test plants were grown for three weeks in a glass greenhouse at 25° C., and the herbicidal activity and the phytotoxicity were evaluated. The results are shown in Tables 10 and 11.

                  TABLE 3                                                          ______________________________________                                                  Herbicidal activity (pre-emergence application)                                Weeds                                                                          barn-                    Crop                                         Comp.  Dosage  yard-  umbrella                                                                              pickerel-                                                                             Van- tooth-                                                                              rice                             (Ex. No.)                                                                             (g/are) grass  plant  weed   dellia                                                                              cup  plant                            ______________________________________                                         1      20      5      5      5      4    3    4                                       10      5      5      5      4    3    4                                       5       5      5      5      4    3    3                                       2.5     5      5      5      4    3    2                                2      20      5      5      5      4    3    4                                       10      5      5      4      4    3    3                                       5       4      5      4      3    3    1                                       2.5     4      5      4      3    2    0                                3      20      5      5      4      4    4    0                                       10      5      5      4      4    4    0                                       5       5      5      4      4    4    0                                       2.5     5      5      4      4    4    0                                       1.2     5      5      4      4    4    0                                       0.6     5      5      4      4    4    0                                       0.3     4      5      4      4    2    0                                14     20      5      5      4      3    4    3                                       10      5      5      3      1    4    3                                       5       5      3      1      0    2    1                                       2.5     5      1      0      0    0    0                                15     20      5      5      5      4    4    4                                       10      5      5      4      3    4    3                                       5       5      5      4      3    3    2                                       2.5     4      4      2      2    2    1                                17     20      5      5      4      4    5    1                                       10      5      5      4      4    4    0                                       5       5      4      2      2    2    0                                       2.5     5      2      1      0    1    0                                18     20      5      5      4      5    4    0                                       10      4      5      3      4    3    0                                       5       3      3      0      2    1    0                                       2.5     3      1      0      0    0    0                                19     20      5      5      5      4    3    4                                       10      5      5      5      4    3    4                                       5       5      5      4      4    3    4                                       2.5     5      4      4      4    2    3                                20     20      5      5      5      3    3    4                                       10      5      5      5      3    3    4                                       5       5      5      4      3    3    3                                       2.5     5      5      4      3    3    2                                21     20      5      5      5      4    4    3                                       10      5      5      5      4    4    2                                       5       5      5      5      4    4    1                                       2.5     5      5      5      4    3    0                                22     20      5      5      5      4    5    4                                       10      5      5      5      4    4    2                                       5       5      5      5      4    4    1                                       2.5     5      5      4      3    4    0                                28     20      5      5      4      4    4    3                                       10      5      5      4      4    4    2                                       5       5      5      4      4    4    1                                       2.5     5      5      4      3    4    0                                30     20      5      5      4      4    4    4                                       10      5      5      4      3    3    3                                       5       5      5      4      3    3    1                                       2.5     5      5      4      3    2    0                                32     20      5      5      5      4    4    3                                       10      5      5      4      4    4    3                                       5       5      5      4      4    4    3                                       2.5     5      5      4      4    4    1                                36     20      5      5      5      4    4    0                                       10      5      5      5      4    4    0                                       5       5      5      5      4    4    0                                       2.5     5      5      4      4    4    0                                37     20      5      5      5      5    5    0                                       10      5      5      5      5    5    0                                       5       5      5      4      4    5    0                                       2.5     5      4      4      4    4    0                                38     20      5      5      5      5    5    1                                       10      5      5      5      4    5    0                                       5       5      5      4      4    4    0                                       2.5     5      5      4      4    4    0                                39     20      5      5      5      4    5    0                                       10      5      5      4      4    4    0                                       5       5      5      4      4    4    0                                       2.5     5      5      4      3    4    0                                40     20      5      5      5      4    4    0                                       10      5      5      5      4    4    0                                       5       5      5      5      4    3    0                                       2.5     5      5      5      3    3    0                                42     20      5      5      5      4    4    0                                       10      5      5      5      4    4    0                                       5       5      5      4      4    4    0                                       2.5     5      5      4      4    4    0                                43     20      5      5      5      5    4    1                                       10      5      5      5      5    4    1                                       5       5      5      5      4    4    1                                       2.5     5      5      4      3    3    1                                47     20      5      5      5      5    5    1                                       10      5      5      4      5    5    1                                       5       5      5      4      5    5    0                                       2.5     5      5      4      4    4    0                                       1.2     5      5      4      4    3    0                                       0.6     5      5      4      4    2    0                                       0.3     5      5      4      3    2    0                                       0.15    3      5      3      2    1    0                                48     20      5      5      4      4    4    0                                       10      5      5      4      4    4    0                                       5       5      5      4      4    4    0                                       2.5     5      5      4      4    4    0                                50     20      4      5      5      3    3    0                                       10      4      5      5      3    3    0                                       5       4      5      5      3    3    0                                       2.5     4      5      4      3    3    0                                51     20      5      5      4      4    5    0                                       10      5      5      4      4    4    0                                       5       5      5      4      4    4    0                                       2.5     5      5      4      4    4    0                                52     20      5      5      4      4    4    0                                       10      5      5      4      4    4    0                                       5       5      5      4      3    4    0                                       2.5     5      5      4      2    4    0                                54     20      5      5      4      4    4    0                                       10      5      5      4      4    4    0                                       5       5      5      3      4    4    0                                       2.5     5      5      2      3    3    0                                55     20      5      5      4      4    4    0                                       10      5      5      4      4    4    0                                       5       5      5      4      4    4    0                                       2.5     5      5      4      4    3    0                                57     20      5      5      5      5    5    1                                       10      5      5      5      5    4    0                                       5       5      5      4      3    4    0                                       2.5     5      5      4      3    3    0                                58     20      5      5      5      4    4    0                                       10      5      5      4      3    4    0                                       5       5      5      4      2    2    0                                       2.5     5      5      3      1    1    0                                73     20      5      5      5      5    5    1                                       10      5      5      5      4    5    0                                       5       5      5      4      4    4    0                                       2.5     5      5      4      4    4    0                                89     20      5      5      5      5    5    4                                       10      5      5      5      5    5    2                                       5       5      5      5      4    5    1                                       2.5     5      5      4      4    4    0                                91     20      5      5      5      4    3    4                                       10      5      5      4      4    3    3                                       5       4      5      4      3    3    1                                       2.5     4      5      4      3    2    0                                98     20      5      5      5      4    4    0                                       10      5      5      5      4    4    0                                       5       5      5      5      3    4    0                                       2.5     5      5      5      3    4    0                                99     20      5      5      5      5    5    1                                       10      5      5      5      5    5    0                                       5       5      5      5      5    4    0                                       2.5     5      5      4      4    4    0                                100    20      5      5      5      5    5    0                                       10      5      5      5      5    5    0                                       5       5      5      5      4    5    0                                       2.5     5      5      4      4    4    0                                Com-   20      5      5      5      5    5    1                                parison                                                                               10      5      5      5      5    5    0                                (1)    5       5      5      5      4    4    0                                       2.5     5      5      4      4    4    0                                       1.2     5      5      3      4    4    0                                       0.6     4-5    5      2-3    4    3-4  0                                       0.3     4-5    5      1-2    3-4  1-2  0                                Com-   20      5      5      4      4    4    0                                parison                                                                               10      5      5      4      4    4    0                                (2)    5       5      5      4      3    4    0                                       2.5     5      5      4      2    2    0                                Com-   20      5      5      4      1    2    0                                parison                                                                               10      4      4      3      0    1    0                                (3)    5       3      5      0      0    0    0                                       2.5     1      4      0      0    0    0                                ______________________________________                                          Note: Activity Ratings; 0 (no damage)  s (complete kill)                 

Comparison (1): butachlor

Comparison (2): ##STR181## (described in EP-A-37938)

Comparison (3): ##STR182## (described in EP-A-18497)

                  TABLE 4                                                          ______________________________________                                                             Herbicidal activity                                        Comp.    Dosage     (pre-emergence application)                                (Ex. No.)                                                                               (g/are)    barnyardgrass                                                                             pickerelweed                                    ______________________________________                                         59       40         5          5                                               60       40         5          5                                               63       40         5          5                                               64       40         5          5                                               66       40         5          5                                               67       40         5          5                                               69       40         5          5                                               71       40         5          5                                               72       40         5          5                                               74       40         5          5                                               75       40         5          5                                               76       40         5          5                                               77       40         5          5                                               78       40         5          5                                               79       40         5          5                                               80       40         5          5                                               81       40         5          5                                               82       40         5          5                                               83       40         5          5                                               85       40         5          5                                               87       40         5          2                                               88       40         5          5                                               90       40         5          5                                               94       40         5          5                                               95       40         5          5                                               97       40         5          5                                               101      40         5          5                                               102      40         5          5                                               103      40         5          5                                               105      40         5          5                                               106      40         5          5                                               107      40         5          5                                               109      40         5          5                                               110      40         5          5                                               112      40         5          5                                               116      40         5          5                                               117      40         5          5                                               118      40         5          5                                               119      40         5          5                                               120      40         5          5                                               123      40         5          5                                               ______________________________________                                    

                                      TABLE 5                                      __________________________________________________________________________              Herbicidal activity (pre-emergence application)                                Weeds                           Crop                                  Comp.                                                                               Dosage                                                                             slender                                                                             water                                                                               perennial  bog   hardstem                                                                            rice                                  (Ex. No.)                                                                           (g/are)                                                                            spikerush                                                                           chestnut                                                                            sedge                                                                               arrowhead                                                                            pondweed                                                                             bulrush                                                                             plant                                 __________________________________________________________________________          20  4    4    4    2     4     5    1                                     3    10  4    4    4    2     4     5    0                                          5   3    4    4    1     4     5    0                                          2.5 3    3    3    0     3     5    0                                          20  5    4    4-5  2     4     5    2                                     47   10  4    3    3-4  2     4     5    1                                          5   4    3    2-3  0     4     5    1                                          2.5 4    2    2    0     4     5    0                                          20  3    3    3    1     4     5    0                                     48   10  3    3    3    1     4     5    0                                          5   3    2    3    1     2     4    0                                          2.5 3    1    2    0     0     4    0                                          20  5    4    4    4     1     5    1                                     Compar-                                                                             10  5    4    4    3     1     5    1                                     ison 5   4    3    4    1     0     5    0                                     (1)  2.5 4    1    3    0     0     5    0                                     __________________________________________________________________________      Comparison (1) is as described above.                                    

                  TABLE 6                                                          ______________________________________                                                  Herbicidal activity (post-emergence application)                               Weeds                                                                          barn-                    Crop                                         Comp.  Dosage  yard-  umbrella                                                                              pickerel-                                                                             Van- tooth-                                                                              rice                             (Ex. No.)                                                                             (g/are) grass  plant  weed   dellia                                                                              cup  plant                            ______________________________________                                         3      20      4      4      4      1    2    0                                       10      4      4      4      1    2    0                                       5       4      4      3      1    2    0                                       2.5     4      4      3      1    2    0                                       1.2     4      3      3      1    2    0                                       0.6     4      2      3      1    2    0                                       0.3     3      2      2      1    2    0                                18     20      4      3      3      1    0    0                                       10      4      3      1      0    0    0                                       5       2      1      0      0    0    0                                       2.5     1      0      0      0    0    0                                22     20      4      4      4      3    4    1                                       10      4      4      4      3    3    1                                       5       4      4      4      2    3    0                                       2.5     4      4      4      2    3    0                                28     20      5      5      4      2    2    2                                       10      5      4      4      2    2    1                                       5       5      4      4      1    1    0                                       2.5     4      3      2      1    1    0                                36     20      4      5      3      2    3    1                                       10      4      4      3      2    3    0                                       5       4      4      3      1    3    0                                       2.5     4      3      3      1    3    0                                37     20      4      4      4      2    3    1                                       10      4      4      4      1    3    0                                       5       4      4      3      1    3    0                                       2.5     3      3      3      1    2    0                                38     20      4      4      4      2    3    2                                       10      4      4      4      2    2    1                                       5       3      4      3      2    2    0                                       2.5     3      4      3      2    1    0                                39     20      4      4      3      3    3    0                                       10      4      3      3      2    2    0                                       5       3      3      2      1    1    0                                       2.5     2      3      2      1    1    0                                40     20      4      4      4      1    3    0                                       10      4      4      3      1    3    0                                       5       4      4      3      1    2    0                                       2.5     4      4      3      1    2    0                                42     20      4      5      4      2    3    1                                       10      4      5      3      2    3    0                                       5       4      5      3      1    2    0                                       2.5     4      4      3      1    2    0                                43     20      4      4      4      1    2    0                                       10      4      4      3      1    2    0                                       5       4      4      2      1    1    0                                       2.5     3      3      2      1    1    0                                47     20      5      5      4      5    3    0                                       10      5      5      4      5    3    0                                       5       4      5      3      5    3    0                                       2.5     4      5      3      4    3    0                                48     20      4      4      4      1    2    0                                       10      4      4      4      1    2    0                                       5       4      4      3      1    2    0                                       2.5     4      3      2      0    2    0                                52     20      4      3      3      1    2    0                                       10      4      3      2      1    2    0                                       5       3      3      2      0    1    0                                       2.5     2      3      2      0    1    0                                57     20      4      4      4      2    3    3                                       10      4      4      4      1    1    1                                       5       4      4      3      1    1    0                                       2.5     4      4      2      0    0    0                                58     20      4      4      4      4    3    0                                       10      4      4      3      3    3    0                                       5       4      4      2      3    3    0                                       2.5     4      4      1      1    1    0                                73     20      4      5      4      4    4    1                                       10      4      5      4      4    4    0                                       5       4      5      4      3    4    0                                       2.5     4      4      3      3    3    0                                89     20      5      5      4      4    4    4                                       10      5      5      4      4    4    3                                       5       4      4      4      3    4    1                                       2.5     4      4      4      3    4    1                                98     20      4      4      4      3    3    0                                       10      4      4      4      3    3    0                                       5       4      4      4      3    3    0                                       2.5     4      3      3      3    2    0                                99     20      4-5    5      4      3    4    0                                       10      4-5    5      3      3    3    0                                       5       4      5      3      3    3    0                                       2.5     4      5      1      2    2    0                                100    20      4-5    5      4      3    4    0                                       10      4-5    5      3      3    4    0                                       5       4-5    5      3      3    3    0                                       2.5     4-5    4      1      2    3    0                                Com-   20      5      4      4      1    3    1                                parison                                                                               10      5      4      3      0    3    0                                (1)    5       5      4      3      0    3    0                                       2.5     5      3      2      0    3    0                                Com-   20      5      5      4      4    4    2                                parison                                                                               10      5      5      4      4    4    1                                (2)    5       5      4      4      4    4    0                                       2.5     4      4      4      3    3    0                                       1.2     4      3      1      0    2    0                                       0.6     4      2      0      0    0    0                                       0.3     2      2      0      0    0    0                                Com-   20      3      4      1      0    1    0                                parison                                                                               10      3      4      0      0    0    0                                (3)    5       2      4      0      0    0    0                                       2.5     0      3      0      0    0    0                                ______________________________________                                          Comparisons (1) to (3) are as described above.                           

                  TABLE 7                                                          ______________________________________                                                                        (post-emergence                                 Comp.   Dosage  Herbicidal activity                                                                           application)                                    (Ex. No.)                                                                              (g/are) barnyardgrass  pickerelweed                                    ______________________________________                                         59      40      5              5                                               60      40      5              5                                               66      40      5              5                                               67      40      5              5                                               69      40      4              3                                               71      40      5              5                                               72      40      5              5                                               74      40      5              4                                               75      40      5              5                                               76      40      5              5                                               77      40      5              5                                               78      40      5              5                                               79      40      5              5                                               80      40      5              5                                               81      40      5              5                                               82      40      5              5                                               83      40      5              4                                               85      40      4              4                                               87      40      3              2                                               88      40      4              3                                               91      40      5              4                                               94      40      5              4                                               95      40      5              3                                               97      40      5              3                                               101     40      4              1                                               102     40      5              5                                               103     40      4              5                                               105     40      5              5                                               106     40      5              5                                               107     40      5              5                                               109     40      4              5                                               110     40      5              5                                               112     40      4              5                                               116     40      5              5                                               117     40      5              5                                               118     40      5              5                                               119     40      5              5                                               120     40      5              5                                               123     40      5              5                                               ______________________________________                                    

                                      TABLE 8                                      __________________________________________________________________________              Herbicidal activity (pre-emergence application)                                Weeds                 Crops                                           Comp.                                                                               Dosage                                                                             large                                                                               barnyard-                                                                            pale  green       soy-                                     (Ex. No.)                                                                           (g/are)                                                                            crabgrass                                                                           grass smartweed                                                                            amaranth                                                                            corn                                                                              wheat                                                                              bean                                                                              cotton                                                                             beet                                                                              rape                                                                              tomato                      __________________________________________________________________________          20  5    5     4     5    3  0   1  0   3  5  5                           1    10  5    5     2     5    3  0   0  0   2  3  3                                5   5    5     2     3    0  0   0  0   0  2  1                                2.5 5    5     0     2    0  0   0  0   0  0  0                                20  5    5     3     5    2  0   1  0   2  2  2                           2    10  4    5     2     4    1  0   0  0   2  2  1                                5   4    4     1     2    0  0   0  0   1  0  1                                2.5 2    2     0     0    0  0   0  0   0  0  0                                20  5    5     3     4    0  0   0  0   0  0  0                           3    10  5    5     2     4    0  0   0  0   0  0  0                                5   5    4     2     4    0  0   0  0   0  0  0                                2.5 4    2     2     4    0  0   0  0   0  0  0                                20  5    5     1     2    0  2   0  0   0  2  2                           14   10  5    3     0     0    0  0   0  0   0  2  1                                5   2    0     0     0    0  0   0  0   0  0  0                                2.5 2    0     0     0    0  0   0  0   0  0  0                                20  5    5     0     3    1  0   0  0   0  0  1                           15   10  5    4     0     1    0  0   0  0   0  0  0                                5   2    1     0     0    0  0   0  0   0  0  0                                2.5 2    0     0     0    0  0   0  0   0  0  0                                20  5    5     0     3    3  2   0  0   2  1  1                           17   10  5    5     0     2    2  1   0  0   1  0  1                                5   3    2     0     0    1  0   0  0   0  0  0                                2.5 2    0     0     0    0  0   0  0   0  0  0                                20  5    5     4     5    3  3   2  0   2  2  2                           19   10  5    5     2     5    2  2   1  0   1  1  1                                5   5    4     0     2    0  0   1  0   0  0  0                                2.5 3    3     0     2    0  0   0  0   0  0  0                                20  5    5     4     5    1  1   1  2   2  2  4                           20   10  5    5     2     5    1  0   0  0   1  0  2                                5   5    4     0     4    0  0   0  0   0  0  0                                2.5 3    4     0     2    0  0   0  0   0  0  0                                20  5    5     2     3    1  1   0  0   0  1  2                           21   10  4    5     2     2    0  1   0  0   0  0  2                                5   4    5     2     2    0  0   0  0   0  0  0                                2.5 4    3     1     2    0  0   0  0   0  0  0                                20  5    5     3     3    2  1   2  1   1  2  3                           27   10  5    5     3     3    0  0   2  0   1  1  2                                5   5    4     2     2    0  0   0  0   0  0  1                                2.5 4    4     1     2    0  0   0  0   0  0  1                                20  5    5     5     5    0  1   1  2   2  3  3                           28   10  5    5     4     4    0  1   1  0   2  2  2                                5   5    5     3     4    0  0   0  0   0  0  0                                2.5 4    4     2     3    0  0   0  0   0  0  0                                20  5    5     5     5    4  2   2  0   2  2  3                           30   10  5    5     3     5    2  2   2  0   2  2  0                                5   5    5     2     5    1  0   0  0   0  2  0                                2.5 5    5     2     0    0  0   0  0   0  2  0                                20  5    5     4     5    3  2   0  1   4  3  5                           32   10  5    5     4     5    0  0   0  1   3  2  4                                5   5    5     3     4    0  0   0  0   2  2  3                                2.5 5    5     2     4    0  0   0  0   0  0  2                                20  5    5     0     3    1  0   0  2   4  2  5                           37   10  5    5     0     3    1  0   0  2   3  1  2                                5   4    4     0     0    1  0   0  2   3  0  2                                2.5 4    3     0     0    0  0   0  0   0  0  2                                20  5    5     3     4    1  2   2  0   2  2  2                           38   10  5    5     2     2    1  2   0  0   2  2  2                                5   5    4     1     2    0  1   0  0   2  1  2                                2.5 4    4     0     2    0  0   0  0   2  1  2                                20  5    5     2     5    2  1   0  0   2  2  0                           42   10  5    4     2     5    1  1   0  0   1  2  0                                5   5    3     0     4    0  0   0  0   0  0  0                                2.5 4    3     0     2    0  0   0  0   0  0  0                                20  5    5     3     3    1  2   1  0   2  2  1                           58   10  4    4     3     2    1  1   0  0   2  2  0                                5   4    3     2     1    0  0   0  0   0  0  0                                2.5 3    2     2     1    0  0   0  0   0  0  0                                20  5    5     4     5    2  2   0  0   2  1  3                           59   10  5    5     3     5    2  1   0  0   2  0  0                                5   5    5     1     4    0  0   0  0   0  0  0                                2.5 4    3     0     4    0  0   0  0   0  0  0                                20  5    5     5     5    3  3   2  0   3  4  4                           62   10  5    5     4     5    2  1   2  0   3  3  4                                5   5    5     3     5    2  0   0  0   2  2  3                                2.5 5    5     2     3    2  0   0  0   1  1  2                                20  5    5     5     5    3  3   4  2   5  4  5                           68   10  5    5     5     5    3  2   2  0   4  4  4                                5   5    5     4     5    2  2   1  0   3  3  3                                2.5 5    5     3     5    0  1   1  0   2  3  2                                20  5    5     4     5    4  2   2  2   3  4  5                           70   10  5    5     4     5    3  2   0  2   3  3  5                                5   5    5     3     5    2  1   0  0   3  2  4                                2.5 5    5     2     5    1  0   0  0   3  1  3                                20  5    5     2     3    2  2   0  0   0  2  2                           74   10  5    5     0     3    1  1   0  0   0  0  2                                5   5    4     0     3    0  0   0  0   0  0  0                                2.5 4    4     0     3    0  0   0  0   0  0  0                                20  5    5     2     2    2  2   0  0   0  2  2                           83   10  5    5     0     0    0  0   0  0   0  1  2                                5   4    3     0     0    0  0   0  0   0  0  0                                2.5 4    3     0     0    0  0   0  0   0  0  0                                20  5    5     3     5    2  0   1  0   2  2  2                           91   10  5    4     2     4    1  0   0  0   2  2  1                                5   4    4     1     2    0  0   0  0   1  0  1                                2.5 2    2     0     0    0  0   0  0   0  0  0                                20  5    5     4     5    4  3   2  2   3  4  5                           92   10  5    5     3     5    3  2   1  1   3  3  3                                5   5    5     3     4    2  2   1  0   3  3  3                                2.5 4    5     3     4    1  2   0  0   2  2  3                                20  5    5     4     5    3  3   3  2   3  4  3                           93   10  5    5     4     5    3  2   2  0   3  4  3                                5   5    5     3     5    2  1   1  0   2  2  3                                2.5 5    5     2     5    0  0   1  0   2  2  3                                20  5    5     3     5    2  2   2  0   2  3  4                           94   10  5    5     2     4    1  0   0  0   0  3  2                                5   4    5     1     4    0  0   0  0   0  2  2                                2.5 4    4     0     3    0  0   0  0   0  2  0                           __________________________________________________________________________

                  TABLE 9                                                          ______________________________________                                                  Herbicidal activity (pre-emergence application)                                Weeds                                                                 Comp.  Dosage  large            pale    green                                  (Ex. No.)                                                                             (g/are) crabgrass                                                                              barnyardgrass                                                                           smartweed                                                                              amaranth                               ______________________________________                                         5      40      5       5        5       5                                      25     40      5       5        5       5                                      57     40      5       5        5       5                                      63     40      5       5        3       3                                      64     40      5       5        2       1                                      67     40      5       5        5       5                                      69     40      5       5        4       5                                      71     40      5       5        4       5                                      72     40      5       5        4       5                                      75     40      5       5        4       5                                      76     40      5       5        5       5                                      77     40      5       5        4       5                                      78     40      5       5        4       3                                      79     40      5       5        3       5                                      80     40      5       5        4       5                                      81     40      5       4        3       4                                      82     40      5       5        4       5                                      84     40      5       5        4       5                                      85     40      5       5        4       3                                      88     40      5       5        4       3                                      89     40      5       5        5       5                                      97     40      4       3        1       2                                      102    40      5       5        0       0                                      105    40      5       5        2       3                                      106    40      5       5        0       0                                      107    40      5       5        1       1                                      109    40      5       4        0       0                                      110    40      5       5        1       4                                      118    40      5       4        4       5                                      119    40      5       5        5       5                                      120    40      5       5        4       5                                      123    40      5       5        4       5                                      ______________________________________                                    

                                      TABLE 10                                     __________________________________________________________________________              Herbicidal activity (post-emergence application)                               Weeds                 Crops                                           Comp.                                                                               Dosage                                                                             large                                                                               barnyard-                                                                            pale  green       soy-                                     (Ex. No.)                                                                           (g/are)                                                                            crabgrass                                                                           grass smartweed                                                                            amaranth                                                                            corn                                                                              wheat                                                                              bean                                                                              cotton                                                                             beet                                                                              rape                                                                              tomato                      __________________________________________________________________________          20  4    4     4     3    2  1   3  2   2  3  4                           28   10  4    4     3     2    2  1   3  2   2  3  3                                5   3    4     2     2    1  0   2  2   2  3  3                                2.5 2    2     2     2    0  0   2  2   2  2  2                                20  4    4     3     4    2  0   3  3   3  4  4                           32   10  4    4     3     4    0  0   3  3   3  3  3                                5   4    4     2     2    0  0   2  2   3  3  3                                2.5 4    4     2     2    0  0   2  2   3  3  3                           __________________________________________________________________________

                  TABLE 11                                                         ______________________________________                                                  Herbicidal activity (post-emergence application)                               Weeds                                                                 Comp.  Dosage  large    barnyard-                                                                              pale    green                                  (Ex. No.)                                                                             (g/are) crabgrass                                                                               grass   smartweed                                                                              amaranth                               ______________________________________                                         5      40      4        4       5       3                                      25     40      4        4       4       4                                      57     40      4        4       4       3                                      63     40      4        4       4       3                                      64     40      4        4       3       2                                      67     40      4        4       5       5                                      69     40      4        4       4       4                                      71     40      4        4       4       3                                      72     40      4        4       4       4                                      75     40      4        4       3       3                                      76     40      4        4       4       4                                      77     40      4        4       4       4                                      78     40      4        4       3       3                                      79     40      4        4       4       3                                      80     40      4        4       3       4                                      81     40      4        4       3       3                                      82     40      4        4       4       3                                      84     40      4        4       3       3                                      85     40      4        4       3       2                                      88     40      3        4       2       2                                      89     40      4        4       4       2                                      97     40      4        3       5       5                                      102    40      4        4       3       2                                      105    40      4        3       3       3                                      106    40      3        4       4       3                                      107    40      4        4       4       4                                      109    40      3        2       2       2                                      110    40      4        4       3       3                                      118    40      4        4       4       4                                      119    40      4        4       4       4                                      120    40      4        4       4       4                                      123    40      4        4       4       4                                      ______________________________________                                     

What is claimed is:
 1. A compound of the formula: ##STR183## in which R is OH, C₁ -C₃ alkoxy or R³ -N-R⁴ ; R_(f) is C₁ -C₃ perfluoroalkyl; R¹ is hydrogen, C₁ -C₆ alkyl, phenyl or phenyl substituted by chloro, fluoro, methyl, methoxy, or methylenedioxy; R² is hydrogen or C₁ -C₃ alkyl; n is an integer of 0 to 2; R³ is hydrogen, or C₁ -C₃ alkyl; R⁴ is C₁ -C₆ alkyl, benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, phenylpropyl, phenyl or phenyl substituted with one or two substituents selected from the group consisting of halogen, C₁ -C₄ alkyl, methoxy, methylthio, methylcarbonyl, trifluoromethyl, nitro and phenyl; or R³ and R⁴ together with the nitrogen atom to which they are attached form 2-methylpiperidino 2-ethylpiperidino, morpholino or pyrrolidino; or a an agriculturally acceptable salt thereof.
 2. A compound of the formula: ##STR184##
 3. A herbicidal composition which comprises as an active ingredient, a herbicidally effective amount of a compound of the formula: ##STR185## in which R is OH, C₁ -C₃ alkoxy or R³ -N-R⁴ ; R_(f) is C₁ -C₃ perfluoroalkyl; R¹ is hydrogen, C₁ -C₆ alkyl, phenyl or phenyl substituted by chloro, fluoro, methyl, methoxy, or methylenedioxy; R² is hydrogen or C₁ -C₃ alkyl; n is an integer of 0 to 2; R³ is hydrogen, or C₁ -C₃ alkyl; R⁴ is C₁ -C₆ alkyl, benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, phenylpropyl, phenyl or phenyl substituted with one or two substituents selected from the group consisting of halogen, C₁ -C₄ alkyl, methoxy, methylthio, methylcarbonyl, trifluoromethyl, nitro and phenyl; or R³ and R⁴ together with the nitrogen atom to which they are attached form 2-methylpiperidino, 2-ethylpiperidino, morpholino or pyrrolidino; or a an agriculturally acceptable salt thereof. 